Wrinkle finish composition



Patented Feb. 5, 1946 UNITED STATES PATENT OFFICE,

WRINKLE FINISH COMPOSITION William A. Waldie, Dayton, Ohio, assignor to New Wrinkle, Inc., Dayton, Ohio, a corporation of Delaware No Drawing. Application May 3, 1939, Serial No. 271,592

13 Claims.

Wrinkle finishes as heretofore made in the art have been compounded from so called wrinkling oils which oils comprise raw Chinawood oil, blown drying oils, such as China wood, linseed, perilla, oiticica, etc. Other paint and varnish oils of the so called non-wrinkling" type, such as soya bean, chia, walnut, hempseed, lumbang, poppy seed, sunflower seed, safflower seed, castor, fish, etc. may be utilized. Large amounts of the non-wrinkling oils, however, cannot be used in the formulation of wrinkle finishes; otherwise the wrinkling of the finish on drying is inhibited. Prior to my invention it has been necessary to use blown or pre-oxidized oils in compounding Wrinkle finishes in order to obtain the most satisfactory results. This was particularly true where wrinkle finishes of sprayable consistency were desired.

The disadvantage of using blown oils lies in their instability. This instability results from the pre-oxidation of the oil which oxidation continues in a progressive manner after termination of the blowing treatment. At the beginning of the treatment the oil is soluble in the conventional petroleum or coal tar solvents but as oxidation progressed the oil becomes increasingly less soluble until finally it precipitates out in a rubber-like mass. This renders the wrinkle composition unfit for use. Wrinkle finish coating compositions comprising blown oil constituents, therefore, cannot be stored for any length of time before use.

It has also been found that in using wrinkle coating compositions made with blown oils 2. wrinkle finish having very fine texture cannot be produced, the tendency being for the finish to form a coarse or heavy textural wrinkle pattern on drying.

It is an object of this invention to compound wrinkle finish compositions which are stable on storing and can be readily modified so as to produce various textural wrinkle patterns upon dry- Another object of this invention is to eliminate the necessity of using blown oils in compounding wrinkling compositions.

Another object of this invention is to provide a. wrinkle varnish or enamel composition which is comparable to similar finishes made using blownoils.

Another object is to provide a wrinkle finish composition which can be blended with wrinkling varnish or pigment ground in drying oil so as to produce a coarse, medium or fine textural wrinkle pattern.

Another object is to compound a wrinkle coating composition comprising wrinkling paint oil to produce a wrinkle finish adapted for brushing or spraying which dries to a very fine textural wrinkle pattern.

Another object is to produce wrinkle. finish compositions which can be mixed with drying oil fatty acids to produce the desired pattern or texture of wrinkle finish.

To eliminate the use of blown oils in the formulation of wrinkle finishes of this invention, I employ a wrinkling varnish base having a typical formula as follows:

Varnish "A-I Modified phenol aldehyde resin ("Amberol or Beckacite") lbs Lead acetate or linoleate lbs 5- 9 Raw China-wood oil gal 15-25 Bodied linseed oil gal 2- 5 Solvent naphtha gal 8-10 T011101 al 18-25 Varnish A-Z Modified phenol aldehyde resin (Amberol" or Beckacite) lbs 100 Lead acetate or linoleate lbs 5- 9 Raw China-wood oil gal..- 12-20 Bodied perilla oil gal 5-10 Solvent nap h I al 8-10 Toluol 7 al 18-25 Varnish "A-3 Modified phenol aldehyde resin (Ambero or Beckacite) lbs 100 Lead acetate or linoleate lbs 5- 9 Raw China-wood oil gal 5-10 Bodied oiticica gal 12-20 Solvent naphtha gal 8-10 Toluol' gal 18-25 In the foregoing varnish formulae the synthetic resins employed are of the oil soluble phenol aldehyde type, typical formulae and method of making which are shown in United States Patents 1,623,901 and 1,632,113.

It will be understood that various other resins may be utilized in place of those mentioned.

' Touol, xylol, petroleum naphtha or coal Resins which are suitable are Kauri, dammar, Congo, "Cumar, pontianak, Manila, Zanzibar, elemi, mastic, copal, sandarac and the like. Further other phenol formaldehyde resins of the rosin, fossil resin and ester gum modified type which are readily compatible with the oil vehicle may be used. Also glycerol phthalic resins of the oil soluble type may be utilized, or mixtures of the above resins.

Other wrinkling paint oils such as poyok, parinarium oils or equivalent oils containing polyconjugated double bond linkage may be substituted for the wrinkling oils mentioned in the formula. The bodied linseed oil employed is the grade known in the trade as varnish linseed."

This product comprises linseed oil which has been processed by heat treating the same between 575 to 600 degrees F. until a desired degree of viscosity is obtained. Similarly the bodied perilla oil utilized has been bodied by heat treating in the same manner as in making bodied linseed oil. The oiticica oil used has been bodied by heat treating to a temperature around 450 to 550 degrees F. for an hour to an hour and a half.

The preferred method of making varnishes A-l, "A-2 and "A-3 is to heat all the China wood oil together with approximately to oi the resin in a vessel to a temperature around 540 degrees F. Thereafter the metallic drier, remainder of the oil and the resin are added. When the resin is dissolved the product can be cooled and thinned with solvent or it can be heated longer to obtain a higher viscosity before thinning.

I have discovered, however, that if the varnish is cooled quickly after the second portion of resin is dissolved, a clear wrinkle varnish can be made having improved spraying and wrinkling properties.- The essential step in making varnishes A-l," "A-2 and A-3 is the sudden chilling or cooling of the heat treated oleoresinous mass immediately at the end of the heat treatment.

' This may be done in any suitable manner such as by the application of cold water or by refrigeration.

This method of making the wrinkle finish comuct which is comparable with that made with blown oils and does not have the disadvantage as regards instability on storing. The heat treatment in making the varnishes, it will be understood, may be varied between a temperature range of 450 to 550 degrees F., depending uponthe particular product desired, but preferably the heating is conducted above 500 degrees F.

though the amount of solvent or thinner added may be the same in both cases.

In making a clear wrinkle composition from the above varnishes A-l, A-2" or A-3 about 2 to 5 per cent of a liquid drier is added to the varnishes. A drier composition which has been found to be very satisfactory for this purpose is as follows:

' Liquid drier "A Cobalt linoleate solid lbs 12-16 China-wood oil fatty acids lbs 8-10 tar solvent gal..

position provides a sprayable wrinkle finish prod- Other examples of utilized are as follows:

Liquid drier "B" 5 Lead linoleate lbs 5-10 'Colbalt acetate lbs 2-6 Linseed oil fatty acids lbs 2-5 China-wood oil fatty acids 1bs 4-6 Toluol, xylol, petroleum naphtha or coal tar solvent. gal

Lz'quid drier "C Lead linoleate lbs Manganese borate llos.- Cobalt acetate lbs Drying oil fatty acids (China-wood oil, linseed, etc.) lbs Toluol, xylol, petroleum naphtha or eoal tar solvent al liquid driers which may be For producing a wrinkle finish composition of the desired textural wrinkle finish pattern the above varnishes A-l, "A-2" and A-3 may be made having relatively low or high viscosities as determined by the Gardner-Holdt standards for varnish. In general the higher the viscosity of the varnish the coarser the texture of the wrinkle finish.

Where a finer textural pattern of wrinkle finish is desired than can be obtained by the use of a low viscosity varnish, a varnish-like solution of drying oil fatty acids may be incorporated in the above varnishes. The following examples are typical:

Varnish B China wood oil fatty acids lbs 8-10 Toluol 0r Xylol gal 1 Varnish C By adding various proportions of varnish B or A-l, A-2" or A-3, the texture or pattern of the wrinkle produced on drying is modified. The higher the proportion of varnish B or C added to the varnishes the finer the texture of the wrinkle finish produced. I

In making pigmented wrinkling enamels the desired color pigment may be ground into the varnishes A-l, A-2 or A-3. Owing, however, to thevolatility of the solvent used in preparing varnishes A-l," A-2 and .A-3- it is v preferable to use a special grinding vehicle for this I purpose. A typical example of this is as follows:

Varnish D Modified phenol aldehyde resin 1 or Beckacite) lbs 100 Lead acetate or linoleate lbs 5-9 Raw China-wood oil gal 15-20 Bodied linseed oil ..gal 2-5 Toluol or xylol gal 8-12 High-boiling petroleum naphtha gal 35-50 (Amberolf Varnish D is made in a like manner as varnishes"A-1, A-2" and A-3 but in this instance the heat treatment is maintained to obtain a heavy'viscosity product. This grinding varnish is then mixed with the conventional paint pigments to make a paste of the desired color. Thereafter it is passed through a paint mill to 6-43 thoroughly disperse the pigment in the vehicle.

varnish C to the low viscosity wrinkle varnishes V As an example 01 a pigmented white paste the following formulae are typical:

' White paste 1-A Titanium oxide ..lbs 8-10 Varnish D gal 1 White paste 1-B Titanium oxide lbs 7-9 Zinc oxide lbs 11 /z Varnish D gal 1 Zinc oxide is added in this instance to inhibit any yellowing tendency on baking.

Green paste l-C Chrome green lbs- 7 Blane fix (BaSOr) lbs 3-4 Varnish D gal 1 wrinkling enamels made with the above pastes would have the following formulae:

White wrinkling Enamel 1 Paste 1-A lbs 2-3 Clear wrinkling varnish A-l, A-2

or "A-3" ga1 White Wrinkling Enamel 2 Paste 1-B "lbs" 2-3 Clear wrinkling varnish A-l," A-2 or A-3 gal.. 1

Green wrinkling enamel Paste l-C lbs 2-3 Clear wrinkling varnishes A-l, A-Z or "A-3 gal 1 In the above formulations where the wrinkling varnish employed is of high viscosity the texture of the wrinkle will be coarser than that produced by a varnish of lower viscosity as heretofore explained. To obtain finer textural wrinkle finish patterns in the case of enamels, I add a paste com- In place of the inert pigments mentioned in the formula it will be understood that other inert materials may be utilized, for example whiting, Surfex (CaCOs) etc. Paste 3 produces a fiat finish due to the use of the aluminum soaps.

In compounding enamels using the above varnishes and pigmented pastes difi'erent wrinkle textures are obtained by incorporating various amounts of the inert paste. There is, however, a limit as to the amount of inert paste which can be incorporated in the varnishes before the film becomes perfectly smooth on drying. The amount depends on the particular inert pigment used in making the paste. When a sufilcient amount of inert paste has been incorporated in the enamel, various amounts of drylng'oil fatty acid varnishes B or C may be added to vary the textural pattern of the wrinkle finish. In this way a wrinkle finish having a textural pattern 50 fine as to be practically invisible to the naked eye can be produced.

In drying the improved wrinkle finish of this invention, articles coated with the coating composition may be made to wrinkle by baking the coating at relatively low or high temperatures. For metallic and imilar surfaces a temperature of to 4'75 degrees may be emploped. For application of the coating on wood, paper and similar materials a somewhat lower temperature on the order of 125 to degrees F. may be used. Ordinarily baking the finish at elevated temperatures accentuates the wrinkling and provides a harder finish. Where a highly elastic film is desired. the addition of small amounts of non-drying orsemi-drying oils, such as castor oil, raw soya bean oil or similar materials may be made. Plasticizers such as dibutyl-phthalate or dicresyl phosphate also may be utilized.

The coating compositions of this invention are useful in the manufacture of various compositions such as varnishes, enamels, linoleum, imitation leather and coatings for paper, metal and the like. Different decorative efiects can be produced by applying the wrinkling compositions and drying or baking them to a hard dry finish.

It will be understood that I desire to comprehend within my invention such modifications as come within the scope of the claims and the in vention.

Having thus fully described my invention, what I claim as new and desire to secure by Letters Patent is:

1. An improved method of making a wrinkle finish comprising the steps of (a) mixing A to of the total amount of resin to be used with the total amount of raw China-wood oil, and heating to a temperature between 450 and 540 F., (b) adding a metallic drier, (c) adding the remainder of the. resin and dissolving the same in the mixture, ((1) rapidly chilling the/liquid without the use of thinners and then adding thinners to produce a spray varnish having low viscosity and superior spray qualities, and thereafter adding a'pigment paste and an inert paste comprising at least one substance selected from the group consisting of magnesium carbonate, diatomaceous earth, and asbestine to produce a fine texture enamel in the finished product.

2. An improved method of making a wrinkle finish comprising the steps of (a) mixing to A of the total amount of resin to be used with the total amount of raw China-wood oil, and

heating to a temperature between 450 and 540 F., (1)) adding lead acetate, (0) adding the remainder of the resin and dissolving the same in the mixture, (d) rapidly chilling the liquid without the use of thinners and then adding thinners to produce a spray varnish having low viscosity and superior spray qualities, and thereafter adding a pigment paste and an inert paste comprising at least one substance selected from the group consisting of magnesium carbonate, diatomaceous earth, and asbestine to produce a fine texture enamel in the finished product.

3. An improved method of making a wrinkle finish comprising the steps of (a) mixing to A. of the total amount of resin to be used with the total amount of raw China-wood oil, and heat bodied linseed oil, and heating to a. temperature between 450 and 540 F., (b) adding 75 lead acetate, (c) adding the remainder of the resin and dissolving the same in the mixture, (d) rapidly chilling the liquid without the use of thinners, and adding thinners to produce a spray varnish having low viscosity and superior spray qualities, and thereafter adding a pigment paste and an inert paste comprising at least one substance selected from the group consisting of magnesium carbonate, diatomaceous earth, and asbestine to produce a fine texture enamel in the finished product.

4. An improved method of making a wrinkle finish comprising the steps of (a) mixing A; to of the total amount of resin to be used with the total amount of raw China-wood oil, and heating to a temperature between 450 and 540 F'., adding a metallic drier, (0) adding the remainder of the resin and dissolving the same in the mixture, (d) rapidly chilling the liquid without the use of thinners, and then adding thinners to produce a spray varnish having low viscosity'and superior spray qualities, incorpo rating in said varnish to produce a finer texture finished product a substance of the class comprising free fatty acids, and thereafter adding a pigment paste and an inert paste comprising at least one substance selected from the group consisting of magnesium carbonate, diatomaceous earth, and asbestine to produce a fine texture enamel in the finished product.

"5.An improved method of making a wrinkle finish comprising the steps of (a) mixing 4 to of the total amount of rosin modified phenol formaldehyde resin to .be used with the total amount of raw China-wood oil, and heating to a temperature between 450 to 540 F., (1;) adding a metallic drier, (0) adding the remainder of the resin and dissolving the same in the mixture, (d)

rapidly chilling the liquid without the use of thinners, and then a spray varnish having low viscosity and superior spray qualitiesfand thereafter adding a pigment paste and an inert paste comprising at least one substance selected from the group consisting of magnesium carbonate, diatomaceous'earth, and asbestine to produce the finished product.

a fine. texture enamel in adding thinners to produce 6. An improved method of makings, wrinkle finish comprising the steps of (a) mixing A to v of the total amount of resin to be used with the total amount of raw China-wood oil and heat bodied linseed oil, and heating to a temperature between 450 and 540 F., (b) adding a metallic drier, (0) adding the remainder of the resin and dissolving the same in the mixture, (d) rapidly chilling the liquid without the use of thinners,-

and then adding thinners to produce a spray varnish having low viscosity and superior spray qualities, and adding a pigment paste and an inert paste of the class consisting of modified phenol aldehyde resin, a drier selected from the class consisting of lead acetate and linoleate, raw China-wood oil, bodied linseed oil, a solvent selected from the class consisting of toluol and xylol, high-boiling petroleum naphtha, the inert paste containing a substance selected from the class consisting of a mixture of magnesium carbonate and diatomaceous earth and asbestine to produce a fine texture enamel in the finished product.

'7. An improved method of making a wrinkle finish comprising the steps of (a) mixing to of the total amount of resin to be used with the total amount of raw China-wood oil, and heating to a temperature between 450 and 540 F., (b) adding lead acetate, (0) adding the rethe resin and dissolving the same in mainder oi the resin and dissolving the same in the mixture, (1) rapidly chilling the liquid with paste and an inert paste of the class consisting of modified phenol aldehyde resin, a drier selected from the class consisting of lead acetate and linoleate, raw China-wood oil, bodied linseed oil, a solvent-selected from the clas consisting of toluol and xylol, high boiling petroleum naphtha, the inert paste containing a substance selected from the class consisting of a mixture of magnesium carbonate and diatomaceous earth and asbestine to produce a fine texture enamel in the finished product.

8. An improved method of making a wrinkle finish comprising the stepsof (a) mixing $4; to of the total amount of resin to be usedwith the total amount of raw China-wood oil and heat bodied linseed oil, and heating to a temperature between 450 and 540 F., (b) adding lead acetate, (0) adding the remainder of the resin and dissolving the same in the mixture, (d) rapidly chilling the liquid without the use of thinners, and then adding thinners to produce a spray varnish having low viscosity and superior spray qualities, adding a, pigment paste and an inert paste of the class consisting of modified phenol aldehyde resin, a drier selected from the class consisting of lead acetate and linoleate, raw China-wood oil, bodied linseed oil, a solvent selected from the class consisting of toluol and xylol, high boiling petroleum naphtha, the inert paste containing a substance selected from the class consisting of a mixture of magnesium carbonate and diatomaceous earth and asbestine to produce a fine texture enamel in the finished product.

9. An improved method of making a wrinkle finish comprising the of the total amount of resin to be used with the total amount of raw China-wood oil, and heating to a temperature between 450 and 540 F., (b) adding a metallic drier, (c) adding the remainderof the resin and dissolving the same in the mixture, (d) rapidly chilling the liquid without the use of thinners, and then-adding thinners to produce a spray varnish having low viscosity and superior spray qualities, and incorporating in said varnish to produce a finer textile finished product, a substance of the class comprising free fatty acids from drying, semidrying, and non-drying oils, adding a pigment paste and an inert paste of the class consisting of modified phenol aldehyde resin, a drier selected from the class consisting of lead acetate and linoleate, raw China-wood oil, bodied linseed oil, a solvent selected from the class consisting of toluol and xylol, high boiling petroleum naphtha, the inert paste containing a substance selected from the class consisting of a mixture of magnesium carbonate and diatomaceous earth and asbestine to produce a fine texture enamel in the finished product.

10. An improved method of making a wrinkle finish comprising the steps of (a) mixing A; to of the total amount of rosin modified phenol formaldehyde resin to be used with the total amount of raw China-wood oil, and heating to a temperature between 450 and 540 F., (b) adding a metallic drier, (0) adding the remainder of the mixture, (d) rapidly chilling the liquid without the use of thinners, and adding thinners to produce a, Spray steps of (a) mixing to bonate' and diatomaceous earth and asbestine to produce a fine texture enamel in the finished product.

11. In the method of making a coating composition adapted to be applied as a film and driedto a hard irregular finish comprising an oleoresinous wrinkling drying varnish having pigmented paste incorporated therewith together 5 with drying oil fatty acids, ner,- the steps comprising plasticizer and thin- (a) mixing /4 to of the total amount of resin to be used with the total amount of raw China-wood and heat-bodied linseed oils and heating to a temperature of between 450 and 540 F., (b) adding a metallic drier, (c) adding the remainder of the resin and dissolving it in the mixture, (d) rapidly chilling the liquid without the adding thinners to produce a spray varnish having low viscosity and superior spray qualities, said product containing 17 to 30 gallons of raw China-:wood oil plus bodied vegetable oils to each 100 lbs. of resin vused.

12. In the method of making a coating composition adapted to be applied as a, film and dried use of thinners and then to a hard wrinkling finish consisting of an oleoresinous w g drying varnish, China-wood oil, heat bodied vegetable oils, a metallic drier, a plasticizing agent consisting-of'dibutyl phthalate a thinner and free fatty acids, the steps comprising (a) f mixing A, to of the total amount of resin tobe used with the total amount of raw China-wood and heat-bodied vegetable oils and heating to a temperature of between 450 and 540 F., (b) adding a metallic drier, (c) adding the remainder of the-resin and'dissolving it in the mixture, (d) rapidly chilling the mixture without the use of thinners, (e) adding thinners to produce a spray varnish having low viscosity and superior spray qualities, and (f) incorporat-x ing in said varnish to produce a finer texture free fatty acids.

13., An improved method of making a sprayable enamel composition which is adapted to be baked to produce a wrinkle finish, comprising heating a mixture of an oil soluble phenol aldehyde resin, raw China-wood oil, boiled linseed oil and metallic drier to a temperature between 450 and 550 F. until a homogeneous solution is produced of the desired consistency, thereafter immediately chilling the mass by application of cold water thereto, thereafter adding thinner to produce a wrinkling varnish of the desired consistency. and then incorporating color pigment and asbestine ground in a portion of said wrinkling varnish to provide an enamel which dries to a fine textural wrinkle finish.

WILLIAM A. WALDIE. 

